Sperm identification is crucial in sexual assault cases. While microscopic analysis is the gold standard for sperm detection, it is a laborious procedure even for trained personnel. Reverse transcription-quantitative ...
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Sperm identification is crucial in sexual assault cases. While microscopic analysis is the gold standard for sperm detection, it is a laborious procedure even for trained personnel. Reverse transcription-quantitative real-time PCR (RT-qPCR) can enhance the screening by detecting sperm-specific mRNA markers, such as protamine 2 (PRM2). This study aimed to develop a one-step RT-qPCR assay targeting PRM2 mRNA. Our assay was capable of detecting as low as 0.01 mu L of semen with high specificity and demonstrated successful detection of PRM2 mRNA in simulated-case samples. Owing to the simple workflow involved, our assay requires <30 min for RNA extraction and <60 min for RT-qPCR. Our assay enables high-throughput sperm screening and offers a promising strategy for enhancing the workflow of sexual assault cases.
The fluoranthene skeleton is a structure often found in natural products and fluorescent materials, and thus developing an operationally simple method for diversity-oriented fluoranthene synthesis is an important rese...
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The fluoranthene skeleton is a structure often found in natural products and fluorescent materials, and thus developing an operationally simple method for diversity-oriented fluoranthene synthesis is an important research topic in organic synthesis. However, existing synthetic methods require harsh reaction conditions or limited substrate applicability or both. Here, we report the room temperature synthesis of substituted fluoranthenes and azafluoranthenes through the cationic Rh(I)/H-8-BINAP complex-catalyzed [2 + 2 + 2] cycloaddition using 1,8-dialkynylnaphthalenes. DFT calculations reveal that the H-8- BINAP ligand stabilizes the intermediates, allowing the room temperature reaction. Among the substrates examined, 1,8-bis(phenylethynyl)naphthalene and diarylacetylenes show high reactivity, contrary to the reactivity predicted by their steric bulkiness. Theoretical and experimental mechanistic studies have demonstrated that the noncovalent interactions of the phenyl groups on both the substrates and the ligand accelerate the present sterically demanding reactions by stabilizing the transition states rather than inducing steric repulsions.
A rhodium(III) complex bearing a 1,3-bis(ethoxycarbonyl)-substituted or an unsubstituted cyclopentadienyl ligand (Cp-E or Cp) significantly accelerates a variety of oxidative C-H bond functionalization reactions. Howe...
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A rhodium(III) complex bearing a 1,3-bis(ethoxycarbonyl)-substituted or an unsubstituted cyclopentadienyl ligand (Cp-E or Cp) significantly accelerates a variety of oxidative C-H bond functionalization reactions. However, the driving force of the acceleration compared with a conventionally used Cp*Rh(III) complex has not been elucidated. Herein, we performed density functional theory (DFT) calculations of the rhodium(III)-catalyzed oxidative C-H bond olefination and annulation reactions using Cp*, Cp, and Cp-E ligands, which revealed that the (CpRh)-Rh-E(III) complex stabilizes transition states of not only a C-H bond activation step but also rate-determining reductive elimination and insertion steps by strong orbital interactions. For the sterically demanding substrates, the less sterically hindered CpRh(III) complex can stabilize the transition states of the reductive elimination step more than the (CpRh)-Rh-E(III) complex. Moreover, the whole reaction pathways were calculated to elucidate the mechanism and selectivity of the oxidative [4 + 2] and [2 + 2 + 2] annulation reactions under cationic and neutral conditions, respectively.
It has been established that an unsubstituted cyclopentadienyl (Cp) Rh(III) complex is an effective catalyst for the oxidative ortho-olefination of phenyl carbamates with both acrylates and styrenes under mild conditi...
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It has been established that an unsubstituted cyclopentadienyl (Cp) Rh(III) complex is an effective catalyst for the oxidative ortho-olefination of phenyl carbamates with both acrylates and styrenes under mild conditions. In addition, diolefination of a protected BINOL (1,1 '-binaphthalene-2,2 '-diol) proceeded in high yields and disubstituted acrylates could participate in this catalysis. Experimental and theoretical mechanistic studies elucidated that an electron-deficient nature of the unsubstituted CpRh(III) complex accelerates both the electrophilic aryl C-H rhodation and the rate-limiting alkene insertion steps.
Photoinduced in situ "oxidation" of half-sandwich metal complexes to "high-valent" cationic metal complexes has been used to accelerate catalytic reactions. Here, we report the unprecedented photoi...
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Photoinduced in situ "oxidation" of half-sandwich metal complexes to "high-valent" cationic metal complexes has been used to accelerate catalytic reactions. Here, we report the unprecedented photoinduced in situ "reduction" of half-sandwich metal [Rh(III)] complexes to "low-valent" anionic metal [Rh(II)] ate complexes, which facilitate ligand exchange with electrondeficient elements (diboron). This strategy was realized by using a functionalized cyclopentadienyl (Cp-A3) Rh(III) catalyst we developed, which enabled the basic group-directed room temperature ortho-C-H borylation of arenes.
It has been established that a newly developed cyclopentadienyl rhodium(III) [(CpRhIII)-Rh-A] complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho-bromination of O-phenyl car...
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It has been established that a newly developed cyclopentadienyl rhodium(III) [(CpRhIII)-Rh-A] complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho-bromination of O-phenyl carbamates with N-bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the Cp-A ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the Cp-A ligand and the carbonyl group of NBS.
Screening for male-derived biological material from collected samples plays an important role in criminal investigations, especially those involving sexual assaults. We have developed a loop-mediated isothermal amplif...
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Screening for male-derived biological material from collected samples plays an important role in criminal investigations, especially those involving sexual assaults. We have developed a loop-mediated isothermal amplification (LAMP) assay targeting multi-repeat sequences of the Y chromosome for detecting male DNA. Successful amplification occurred with 0.5 ng of male DNA under isothermal conditions of 61 to 67 A degrees C, but no amplification occurred with up to 10 ng of female DNA. Under the optimized conditions, the LAMP reaction initiated amplification within 10 min and amplified for 20 min. The LAMP reaction was sensitive at levels as low as 1-pg male DNA, and a quantitative LAMP assay could be developed because of the strong correlation between the reaction time and the amount of template DNA in the range of 10 pg to 10 ng. Furthermore, to apply the LAMP assay to on-site screening for male-derived samples, we evaluated a protocol using a simple DNA extraction method and a colorimetric intercalating dye that allows detection of the LAMP reaction by evaluating the change in color of the solution. Using this protocol, samples of male-derived blood and saliva stains were processed in approximately 30 min from DNA extraction to detection. Because our protocol does not require much hands-on time or special equipment, this LAMP assay promises to become a rapid and simple screening method for male-derived samples in forensic investigations.
Organoboron and organosilicon compounds have potential applications in various fields including materials science and medicinal chemistry. Here the authors report a protocol that enables the dearomative carbo-sila-bor...
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Organoboron and organosilicon compounds have potential applications in various fields including materials science and medicinal chemistry. Here the authors report a protocol that enables the dearomative carbo-sila-boration of quinolines. Organoboron and organosilicon compounds are used not only as synthetic building blocks but also as functional materials and pharmaceuticals, and compounds with multiple boryl and silyl groups are beginning to be used for these purposes. Especially in drug discovery, methodology providing easy stereoselective access to aliphatic nitrogen heterocycles bearing multiple boryl or silyl groups from readily available aromatic nitrogen heterocycles would be attractive. However, such transformations remain challenging, and available reactions have been mostly limited to dearomative hydroboration or hydrosilylation reactions. Here, we report the dearomative triple elementalization (carbo-sila-boration) of quinolines via the addition of organolithium followed by photo-boosted silaboration, affording the desired products with complete chemo-, regio-, and stereoselectivity. The reaction proceeds via the formation of silyl radicals instead of silyl anions. We also present preliminary studies to illustrate the potential of silaboration products as synthetic platforms.
A 73-year-old woman was diagnosed with ventricular free wall rupture following acute myocardial infarction. The lesion was repaired with laser coagulation, fibrinogen-thrombin glue application, and patch reinforcement...
A 73-year-old woman was diagnosed with ventricular free wall rupture following acute myocardial infarction. The lesion was repaired with laser coagulation, fibrinogen-thrombin glue application, and patch reinforcement. Five years after surgery, the patient was in New York Heart Association class I.
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